Photographic element containing a phosphoric acid ester of a butynediol-alkylene oxide condensate

ABSTRACT

A photographic element having incorporated in the lightsensitive silver halide emulsion layer or in a colloid layer contiguous therewith a phosphoric acid ester of a condensation product of an alkylene oxide with a butynediol.

United States Patent lnventors E. Scudder Mackey Binghamton, N.Y.; FritzDersch, Binghamton, N.Y.; Fred S. Eiseman, Maplewood, NJ. Appl. No.697,323 Filed Jan. 12, 1968 Patented Oct. 26, 1971 Assignee GAFCorporation New York, N.Y.

PHOTOGRAPHIC ELEMENT CONTAINING A PHOSPIIORIC ACID ESTER OF ABUTYNEDIOL- ALKYLENE [50] Field Search 96/107,

[ References Cited UNITED STATES PATENTS 3,255,013 6/1966 Dersch et al96/107 FOREIGN PATENTS 1,015,023 l2/l965 Great Britain 96/107 PrimaryExaminer- Norman G. Torchin Assistant Examiner-Richard E. FichterAttorneys-George L. Tone and Walter G. Hensel ABSTRACT: A photographicelement having incorporated in the light-sensitive silver halideemulsion layer or in a colloid layer contiguous therewith a phosphoricacid ester of a condensation product of an alkylene oxide with abutynediol.

PHOTOGRAPHIC ELEMENT CONTAINING A PHOSPHORIC ACID ESTER OF A BUTYNEDIOL-ALKYLENE This invention relates to photographic emulsions and, moreparticularly, to the sensitization of these emulsions by incorporatingtherein certain phosphoric acid esters of polyoxyalkylene derivatives ofbutynediols.

Sensitization of silver halide emulsions by the use of polyoxyalkyleneor polyalkylene oxides is well known and is described in US. Pat. Nos.2,423,549 and 2,441,389 while the use of various derivatives ofpolyalkylene oxides as, for example, condensation products of analkylene oxide with glycols is described in US. Pat. Nos. 2,240,472.

A deleterious effect with the use of these materials is their tendencyto increase fog which is defined as the loss of sensitivity of theemulsion, during storage, resulting from the spontaneous occurrence of adevelopable species without exposure to light. Since the intensity ofthe resulting fog is dependent on both the inherent qualities of theemulsion and on the conditions of subsequent processing, the fogquantity becomes dependent, under constant conditions of development, onchanges in such storage variables as time, temperature and relativehumidity. Fog can also be the result of conditions present inhigh-temperature processing.

Since the addition of sensitizer compounds causes an increase in fogduring storage, their use had been somewhat limited especially under theaforesaid conditions of high temperature and humidity storage or underconditions of hightemperature processing. This had led to the need forspecial and somewhat exotic antifoggant compounds for use with thesematerials (see US. Pat. Nos. 2,704,716, 2,716,062 and 2,728,666). In alater development, described in US. Pat. No.

' 3,255,013, the use of certain polyoxyalkylene derivatives ofbutynediols was described in which conventional antifoggants weresuitable since these compounds did not cause an excessive increase infog on storage.

It is an object of this invention, therefore, to provide novelsensitizers for silver halide emulsions.

It is a further object of this invention to provide such sensitizerswhich prevent formation or, at least, minimize fog development onstorage and/or subsequent processing under conditions of hightemperature.

It is also an object of this invention to provide such sensitizercompounds which reduce the development of surface static charges.

In accordance with this invention it has been found that certainphosphoric acid esters of the aforesaid polyoxyalkylene derivatives of abutynediol as hereinafter describedeither prevent formation of orsubstantially curtail fog development without any sacrifice ofsensitivity. This is especially true where film is subject to storageand/or subsequent processing at high temperature.

Therefore this invention is based at least in part in the discovery thatcompounds of the phosphoric ester are satisfactory sensitizers forsilver halide emulsions which do not cause excessive fog on development.

This invention is also based at least in part on the discovery .that theincorporation of these compounds into silver halide emulsions results increases in film speed (i.e., a marked increase in density for a givenexposure) and improvement in the covering power of the developed silver.The covering power is defined as the ratio of the optical density atmaximum density to the weight of silver per square decimeter in thedeveloped image layer.

This invention is also based at least in part on the discovery that theincorporation of these compounds into silver halide emulsions results ina marked reduction in the development of surface static charge.

The phosphoric esters employed in photographic emulsions in accordancewith this invention are compounds of the general formula:

wherein:

R is an alkylene group of from two to aboutfour carbon atoms,

such that the compound can be either a mono-, dior triester ofphosphoric acid, or a mixture of the three, and m and n are positiveintegers such that the molecular weight of the ensuing compound is inexcess of 300 and up to 150,000 or more.

The procedure below describes the preparation of a preferred phosphoricacid ester of a polyoxyalkylene derivative of butynediol.

Procedure A Preparation of the phosphoric acid ester of the condensationproduct of ethylene oxide with l,4-diisobutyl-l,4- dimethyl-butynediol.v

Two hundred grams of a condensation product of ethylene oxide with1,4-diisobutyl-l ,4-dimethyl butynediol having a molecular weight ofabout 600 (and sold under the trademark Surfynol 465) were admixed atroom temperature with 1 gram of hypophosphorous acid. Eleven grams ofphosphorus pentoxide were added slowly over a 1-hour period within atemperature range of 2550." C. The system was then flushed with, andmaintained under a blanket of, nitrogen, while the temperature wasraised to -95 C. After 4 hours, the system was cooled to 75 C., 2 gramsof hydrogen peroxide (35 percent solution) were added and thetemperature was again raised to 90-95 C. for 15 minutes. The system wasthen cooled and the reaction product was decanted from the blackresidue. The product composition, a mixture of mono and diester andnonionic material, was determined from Acid Number values. A typicalproduct from a 4:1 mole ratio of surfactant to phosphorus pentoxide'assays 34.8 percent monoester and 17.6 percent diester.

The aforesaid improvements can berealized by incorporating suchphosphoric acid esters in the light-sensitive silver halide emulsionitself or in the undercoating, substratum, intermediate coating,overcoating or surface coating.

The phosphoric acid esters may also be advantageously employed invarious types of photographic silver halide emulsions, e.g.,nonsensitized emulsions, orthochromatic, panchromatic and X-rayemulsions. If used with sensitizing dyes, the ester material may beadded to the emulsion before or after the dyes are added. Various silverhalides may be used as the light-sensitive component, such as silverbromide, silver iodide, silver chloride or mixed silver halides. Thephosphate esters may be used in emulsions intended for black-and-whitephotography or color photography, e.g., emulsions containingcolor-forming components. For the emulsion for color photography, adeveloper compound of the primary aromatic amine type as, for example,dimethyl aininoaniline should be incorporated with a suitablecolor-forming compound having a group such as hydroxyl or methylene tocouple with the oxidizer group of the developer in the emulsion.

The dispersing agent in the photographic emulsion may be gelatin or someother hydrophilic compound, such as collodion, albumen, methylcellulose, polyvinyl alcohol, polyvinylpyrrolidone or the like.

The quantity of the phosphate ester added to the emulsion will depend toa large extent on the layer into which it is incorporated. In any event,the concentration range, dependent on additive location, is from 0.5 to15 grams per mole of silver halide.

Several examples are set forth below to illustrate the nature of theinvention and the manner of carrying it out. However, the inventionshould not be considered as being limited to the details thereof.

EXAMPLES l-3 These examples illustrate the effectiveness of compounds ofthe type described above in increasing the speed of silver halideemulsions without any resultant increase in fog.

A gelatin-silver halide emulsion in which the silver halide consists of4 percent silver iodide and 96 percent silver bromide was prepared in aconventional manner and brought up to its maximum light sensitivity. itwas then readied for coating on film base, that is, melted at 40 C. andnecessary coating finals were added as, for example, sensitizing dyes,antifoggants, surfactants such as saponin and hardeners such asformaldehyde. A 10 percent aqueous solution of a phosphoric ester of acondensation product of ethylene oxide and 1,4-butynediol having amolecular weight of about 500 was prepared and 10 cc. of this solutionwere added to a sample of the above-described emulsion, containing about0.4 mol of silver halide. A sample of the same emulsion, but notcontaining the phosphoric acid ester, served as control. The so-preparedemulsion samples were coated on a suitable cellulose ester film base anddried. Samples of these film coatings were then exposed in a Type I-BSensitometer and developed in a developer of the following composition:

Distilled water 500 ml.

Metol 2.2 grams Sodium sulfile, anhydrous 72.0 grams Hydroquinone 8.8grams Sodium carbonate, monohydrated 56.0 grams Potassium bromide l4.0grams Water to make l liter.

The results are tabulated below:

Phosphoric acid ester, Relative Fog Example grams speed Density 2density 3 1 Control. 2 After 6' dev.

After 6 days oven test and 6 dev.

EXAMPLES 4-7 Polyethylene oxide Phoslauryl phoric ether, ester, Rel. FogExample grams grams speed Density 2 density a 1 Control. After 6' dev.After 1 day at 140 F. and 50% R.H. and 6 dev.

EXAMPLES 8-9 These examples illustrate the effectiveness of thephosphoric ester compounds when added to other than the emulsion layer.

A gelatin-silver halide emulsion in which the silver halide consists of4 percent silver iodide and 96 percent silver bromide was prepared in aconventional manner. it was then readied for coating on film base, thatis, melted at 40 c. and necessary coating finals were added such assensitizing dyes, stabilizers and hardeners. The so-prepared emulsionsamples 'were coated on a suitable cellulose ester base and dried. A 2percent aqueous gelatin solution containing 6 percent (on weight of drygelatin) of the phosphoric acid ester described above in examples l-3was coated on the emulsion side of the film base as an anti-abrasionlayer. A sample of the same emulsion coated film base was also coatedwith an anti-abrasion layer consisting of a 2 percent aqueous gelatinsolution without the phosphoric acid ester. After drying, the filmsamples were exposed and processed as described in examples l-3 above.The results are tabulated below:

Relative Fog Example Anti-abrasion coating speed Density 1 density 1 82% gelatin solution 150 0.13 O. 20

plus 0.12% of phosphoric acid ester. 9 2% gelatin solution.. 100 0. 180.30

1 After 6 dev. 2 After 6 days oven test and 4' dev.

The data tabulated below list the results of measurements made onsurface resistivity. Since these measurements are indicative of thestatic susceptibility of the film surface, they noncurl emulsionformulations prepared in the conventional manner. Phosphate esters withthe condensation products of ethylene oxide andl,4-diisobutyl-l,4-dimethylbutynediols in which the molecular weightswere 500 (Surtynol440) and 600 (Surtynol 465), respectively, wereevaluated.

All samples contained 6 percent of the phosphate ester of a Surfynol(based on dry gelatin) and were conditioned for 12 hours at 72 F. and 50percent relative humidity. Resistivity was determined using a MegohmMeter. The results are tabuiated below.

Phosphate Surface Example Ester Added Resistivity (Meg.)

10 Control l2Xl0 l l Phosphate Ester of Surl'ynol 440 2.6Xl0 l2Phosphate Ester of Surfynol 465 1.900

While exemplary embodiments of the invention have been described, thetrue scope of the invention is to be determined from the followingclaims.

What is claimed is:

wherein R is an alkylene group of from two to about four carbon atoms, RR,, R and R are members selected from the group consisting of hydrogenand an alkyl group of from one to about five carbon atoms, X is a memberselected from the group consisting of hydrogen and the polyoxyalkylenederivative group as set forth in the general fonnula and m and n arepositive integers such that the molecular weight of the ensuing compoundis in excess of 300 and up to 150,000 or more.

2. The photographic element as defined in claim 1 wherein the phosphoricester is a compound having the following formula:

(!)x H: H: OX

wherein m and n represent integers providing a molecular weight of atleast 750, and X is a member selected from the group consisting ofhydrogen and the polyoxyalkylene derivative group as set forth in theformula 3. The photographic element as defined in claim 2 wherein thephosphoric ester is the monoester.

'4. The photographic element as defined in claim 2 wherein thephosphoric ester is the diester.

5. The photographic element as defined in claim 2 wherein the phosphoricester is the triester.

6. The photographic element as defined in claim 2 wherein the phosphoricester is a mixture of the mono-, diand triesters.

7. The photographic element as defined in claim 1 wherein the phosphoricester is located in the silver halide emulsion.

8. The photographic element as defined in claim 1 wherein the phosphoricester is located in the surface coating layer.

9. The photographic element as defined in claim 1 wherein saidphosphoric ester product is employed in an amount of from about 0.5 to15 grams per mole of silver halide.

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,615,612 Dated 10/ 26/71 Inventol-(s) E. Scudder Mackey, Fritz Dersch,Fred S. Eiseman It is certified thaterror appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

In Title after "Butynediol-Alkylehe" add --Oxide Condensate Signed andsealed this 9th day of May 1972.

(SEAL) Attest:

EDWARD ILFLETCHEILJR. ROBERT GOTTSCHALK Actesting Officer Commissionerof Patents

2. The photographic element as defined in claim 1 wherein the phosphoricester is a compound having the following formula: wherein m and nrepresent integers providing a molecular weight of at least 750, and Xis a member selected from the group consisting of hydrogen and thepolyoxyalkylene derivative group as set forth in the formula
 3. Thephotographic element as defined in claim 2 wherein the phosphoric esteris the monoester.
 4. The photographic element as defined in claim 2wherein the phosphoric ester is the diester.
 5. The photogrAphic elementas defined in claim 2 wherein the phosphoric ester is the triester. 6.The photographic element as defined in claim 2 wherein the phosphoricester is a mixture of the mono-, di- and triesters.
 7. The photographicelement as defined in claim 1 wherein the phosphoric ester is located inthe silver halide emulsion.
 8. The photographic element as defined inclaim 1 wherein the phosphoric ester is located in the surface coatinglayer.
 9. The photographic element as defined in claim 1 wherein saidphosphoric ester product is employed in an amount of from about 0.5 to15 grams per mole of silver halide.